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Train from Barcelona to San Sebastian

What is the best time and method to purchase train tickets for June 5? Will also need tickets from SS TO MADRID On the 8th

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From Barcelona to San Sebastian here are two direct trains per day, around 7:30 and 15:30, which take about 5.5 hours. Schedule options are similar from San Sebastian to Madrid Chamartín station, with fast morning or evening trains also taking 5.5 hours. However, confirmed schedules are not yet published for your first route on June 5, so I'd look again in a week or two. www.renfe.es and outside agents like trainline.eu and raileurope.com already have the second ticket for sale with advance discount.